Department Civil, Mining and Process Engineering

Course Code HMT711S – Hydrometallurgy 314

Programme BEng Chemical

Assessment Practical Lab 2 – Thermodynamics and Kinetics of leaching

Due date 22 May 2025

Group

Student number: 223118419

Surname, First names: Mushambadope Patrick.T
Lecturer: Dr. T. Nghipulile
Lab Technician(s): Christiaan Jonathan

Abstract
This experiment uses sulfuric acid to study the thermodynamics and kinetics of zinc oxide
leaching, with an emphasis on how temperature and acid concentration affect dissolving
rates. (Binnemans & Jones, 2023)The thermodynamic viability of zinc leaching under various
circumstances is predicted using Eh-pH diagrams, and kinetic analysis entails performing
leach tests at various temperatures and acid concentrations (0.02–0.1 M H₂SO₄) (Mukherjee,
Mukhopadhyay, Hashim, & Gupta, 2014).
Atomic absorption spectroscopy (AAS) is used to measure the concentration of zinc in
solution over time, producing the dissolution profiles. The rate-controlling mechanism
(diffusion vs. chemical reaction) is clarified by using Arrhenius plots to compute activation
energy and the starting rate technique to establish the reaction order and rate constant (Ploetz,
Engelke, Lächelt, & Wuttke, 2020).
The kinetic data fits a first-order model, and the results show a direct relationship between
acid concentration and leaching rate. The stability of zinc species in acidic conditions is
confirmed by thermodynamic analysis, which agrees with experimental findings. The study
offers insights for improving industrial leaching operations by highlighting the interaction
between kinetic realities and thermodynamic forecasts in hydrometallurgical processes.

Contents
Abstract............................................................................................................... 2
1. Introduction.................................................................................................. 3

1
2. Aims and Objectives................................................................................... 3
3. Materials and Apparatus............................................................................4
3.1 Materials and reagents........................................................................... 4
3.2 Apparatus.............................................................................................. 4
4. Procedure..................................................................................................... 4
5. Results.......................................................................................................... 5
5.1 Sample calculations................................................................................ 5
5.2 Effect of acid concentration at (Temperature 30°C) Log[rate] and
Log [H2SO4]........................................................................................................ 6
5.3 Effect of temperature on leaching rate at constant concentration. 7
6. Discussion of results................................................................................. 11
7. Conclusion.................................................................................................. 11
8. Recommendations..................................................................................... 12
9. References.................................................................................................. 13

Figure 1-log(rate) vs log [H2SO4] at T = 35 °C....................................................6

Figure 2-Log(Rate) vs Log(K) at C= 0.02M.............................................................7
Figure 3-Log(Rate) vs Log(K) at C= 0.05M.............................................................8
Figure 4-Log(Rate) vs Log(K) at C= 0.08M.............................................................9
Figure 5-Log(Rate) vs Log(K) at C= 0.1M.............................................................10

Table 1-Effect of acid concentration(temperature of 30℃.)...................................5

Table 2-Effect of acid concentration(temperature of 35℃.)...................................5
Table 3-Effect of acid concentration(temperature of 40℃.)...................................5
Table 4-Effect of acid concentration(temperature of 45℃.)...................................6
Table 5-Log(rate) and log[H2SO4] at 35℃.............................................................6
Table 6-Log[K] and log[rate] at different temperatures at a constant
concentration of 0.02M.......................................................................................... 7
Table 7-Log[K] and log[rate] at different temperatures at a constant
concentration of 0.05M.......................................................................................... 8
Table 8-Log[K] and log[rate] at different temperatures at a constant
concentration of 0.08M.......................................................................................... 9
Table 9-Log[K] and log[rate] at different temperatures at a constant
concentration of 0.1M............................................................................................ 9

1. Introduction
2
Leaching is a basic hydrometallurgical process that uses aqueous reagents to recover precious
metals from ores. Both kinetic and thermodynamic feasibility affect its effectiveness. (Paiva,
2023).
Eh-pH diagrams ensure spontaneous reactions by thermodynamically predicting stable
species and ideal leaching conditions. The dissolving reaction controls sulfuric acid leaching
for zinc oxide.: ZnO + H₂SO₄ → ZnSO₄ + H₂O. However, kinetics—which is impacted by
temperature, surface area, and acid concentration—determines the extraction rate.In order to
assess kinetic behavior, this experiment looks at zinc dissolution at regulated acid
concentrations (0.02–0.1 M H₂SO₄). By presuming a constant reactant concentration during
the early phases of a reaction, the initial rate technique streamlines the process of determining
the rate law. (El-Azazy, Min, & Annus, 2020).
At the same time, experimental conditions inside the water stability region are validated by
thermodynamic analysis utilizing Eh-pH diagrams. Zinc in solution is quantified using atomic
absorption spectroscopy, which makes it possible to create dissolution-time profiles. For
industrial applications, where quick leaching with low reagent usage is preferred, an
understanding of these concepts is essential. The impact of activation energy on rate control
and challenges such departures from ideal models (such as diminishing core assumptions) are
also examined. This paper provides a framework for metal recovery process optimization by
fusing thermodynamic and kinetic analysis, bridging theoretical predictions with real-world
results.

2. Aims and Objectives

 Investigate the effect of sulfuric acid concentration: on the zinc oxide dissolution
rate to determine the correlation between leaching efficiency and reagent strength.
 Determine the reaction order and rate constant: utilizing kinetic data analysis and
the initial rate approach.
 Apply thermodynamic principles (Eh-pH diagrams): to confirm experimental
findings and forecast practical leaching conditions.
 Calculate activation energy :via Arrhenius plots to identify whether the leaching
process is diffusion- or chemically controlled.
 Evaluate practical limitations : of kinetic assumptions and thermodynamic models
in actual leaching systems.
 Develop dissolution-time profiles: to see the kinetics of zinc extraction at different
acid concentrations.

3. Materials and Apparatus

3.1 Materials and reagents
 Zinc metal pieces
 Sulfuric acid (AR)
 Distilled water

3
 3.2 Apparatus
 Glass beaker, 200 ml
 Water bath
 Stirrer with temperature control
 Magnetic follower
 Thermometer (0 – 100°C)
 AAS

4. Procedure
1. Four stock solutions of sulfuric acid (0.02 M, 0.05 M, 0.08 M and 0.10 M) were
prepared in separate 100 mL volumetric flasks and maintained in a water bath at the
target temperature.
2. Four zinc pieces were weighed and each piece was measured to determine the area of
one face (only one side was measured to standardize the exposed surface area for
comparison). Each sample was clearly labelled to track its use in the corresponding
experiment.
3. A magnetic stirrer bar was placed into a beaker. The first acid solution was poured
into the beaker, stirred at 500 rpm and heated until the desired temperature was
reached (35o C ).
4. The designated zinc piece was added to the stirred solution, and the reaction timer
was started.
5. The leaching reaction was allowed to proceed for 15 minutes.
6. At the end of the 15 minutes, a 1 mL aliquot was withdrawn using a pipette.
7. The withdrawn sample was diluted as required and submitted for analysis by atomic
absorption spectroscopy (AAS).
8. Steps 3–7 were repeated for each of the remaining stock solutions, using a fresh zinc
piece for each run.

5. Results
5.1 Sample calculations

Table 1-Effect of acid concentration(temperature of 30℃.)

[H2SO4] Mass of Zn Area of Zn Zinc conc in Mass of Rate

sample (g) sample ( soln (g/l) zinc (g/m2 s)
2
mm ¿ leached (g)
0.02M 0.8312 116 0.01191 0.0016 0.0153
0.05M 0.9118 156 0.0861 0.0070 0.0499
0.08M 0.9122 104 0.0355 0.0039 0.0417

4
0.1M 0.7070 98 0.03826 0.0055 0.0624

Table 2-Effect of acid concentration(temperature of 35℃.)

[H2SO4] Mass of Zn Area of Zn Zinc conc in Mass of Rate

sample (g) sample ( soln (g/l) zinc (g/m2 s)
2
mm ¿ leached (g)
0.02M 0.7699 174 0.02163 0.0024 0.01532
0.05M 0.6834 134 0.02751 0.0026 0.02155
0.08M 0.7822 90 0.07445 0.0079 0.09753
0.1M 0.4216 54 0.04698 0.0045 0.09259

Table 3-Effect of acid concentration(temperature of 40℃.)

[H2SO4] Mass of Zn Area of Zn Zinc conc in Mass of Rate

sample (g) sample ( soln (g/l) zinc (g/m2 s)
2
mm ¿ leached (g)
0.02M 0.1841 38 0.02339 0.0013 0.03801
0.05M 0.1302 50 0.00684 0.0004 0.00889
0.08M 0.2797 64 0.07977 0.0041 0.07118
0.1M 0.2399 66 0.01093 0.0006 0.01010

Table 4-Effect of acid concentration(temperature of 45℃.)

[H2SO4] Mass of Zn Area of Zn Zinc conc in Mass of Rate

sample (g) sample ( soln (g/l) zinc (g/m2 s)
2
mm ¿ leached (g)
0.02M 0.3130 64 0.00850 0.0015 0.02604
0.05M 0.5331 100 0.04398 0.0050 0.05556
0.08M 0.4328 76 0.02990 0.0015 0.02193
0.1M 0.4377 52 0.05040 0.0043 0.09188

5.2 Effect of acid concentration at

(Temperature 30°C) Log[rate] and Log
[H2SO4]

5
Table 5-Log(rate) and log[H2SO4] at 35℃.

[H2SO4] log[H2SO4] Rate log(Rate)

(g/m2 s )

0.02M -1.69897 0.01532 -1.81474

0.05M -1.30103 0.02155 -1.66655
0.08M -1.09691 0.09753 -1.01086
0.1M -1.00000 0.09259 -1.03344

log(Rate) vs log[H2SO4] at 35℃.

0
-0.2
-0.4
-0.6
log(Rate)

-0.8
-1
-1.2 f(x) = 1.22608131304456 x + 0.180908617331332
-1.4 R² = 0.820120970262559
-1.6
-1.8
-2
-1.8 -1.7 -1.6 -1.5 -1.4 -1.3 -1.2 -1.1 -1 -0.9

log[H2SO4]

Figure 1-log(rate) vs log [H2SO4] at T = 35 °C

Determination of value of k and n:

The values of k and n can be determined from the initial rate method
expressed as: Log (initial rate) = n log ([A]) + log k

Where n is the gradient

Log(k) is the y intercept
Therefore from figure1, log (k) = 0.1809
0.1809
k =10
=1.5167
n= 1.2261

5.3 Effect of temperature on leaching rate at

constant concentration
(C= 0.02M):
Table 6-Log[K] and log[rate] at different temperatures at a constant concentration of 0.02M.

Temperature(¿ 0 C)¿ Temperature 1/T Rate (g/m 2 s ) ln(Rate)

) at 0.02M (K)at 0.02M

6
 30 303 0.0033003 0.01530 -4.17990
35 308 0.0032468 0.01532 -4.17860
40 313 0.0031949 0.03801 -3.26991
45 318 0.0031447 0.02604 -3.64812

ln(Rate) vs 1/T at C=0.02M

0.00000
-0.50000
-1.00000
-1.50000
ln(Rate)

-2.00000
-2.50000
-3.00000
-3.50000
f(x) = − 4847.61690020939 x + 11.7982244410192
-4.00000 R² = 0.536075770176446
-4.50000
0.0031 0.00315 0.0032 0.00325 0.0033 0.00335

1/T

Figure 2-ln(Rate) vs 1/T at C=0.02M

Values of K and n
Log(initial rate)= nlog[A] + log[K]
Y=15.584 x -40.493
Log K= -40.493
K=10−40.493

K=3.2137 ×10−41
n= 15.584

(C= 0.05M):

Table 7-Log[K] and log[rate] at different temperatures at a constant concentration of 0.05M.

Temperature(¿ 0 C)¿ Temperature 1/T Rate (g/m 2 s ) ln(Rate)

) at 0.05M (K)at 0.05M
30 303 0.0033003 0.04990 -2.99773
35 308 0.0032468 0.02155 -3.83738
40 313 0.0031949 0.00889 -4.72283
45 318 0.0031447 0.05556 -2.89029

7
 ln(Rate) vs 1/T at C=0.05M
0.00000
-0.50000
-1.00000
-1.50000
ln(Rate)

-2.00000
-2.50000
-3.00000
-3.50000
-4.00000 f(x) = 1250.02135351083 x − 7.63919770932706
R² = 0.00963856862756118
-4.50000
-5.00000
0.00310 0.00315 0.00320 0.00325 0.00330 0.00335

1/T

Figure 3- ln(Rate) vs 1/T at C=0.05M

Values of K and n
Log(initial rate)= nlog[A] + log[K]
Y=-3.7625 x + 7.8074
Log K= 7.8074
K=107.8074

K=6.4180 ×107
n= -3.7625

(C= 0.08M):

Table 8-Log[K] and log[rate] at different temperatures at a constant concentration of 0.08M.

Temperature(¿ 0 C)¿ Temperature 1/T Rate (g/m 2 s ) ln(Rate)

) at 0.08M (K)at 0.08M
30 303 0.0033 0.04170 -3.17725
35 308 0.0032 0.09753 -2.32760
40 313 0.0032 0.07118 -2.64254
45 318 0.0031 0.02193 -3.81990

8
 ln(Rate) vs 1/T at C=0.08M
0.00000
-0.50000
-1.00000
-1.50000
-2.00000
ln(Rate

-2.50000
-3.00000 f(x) = 4195.65599319022 x − 16.5087850571811
-3.50000 R² = 0.184709974432023
-4.00000
-4.50000
0.0031 0.0032 0.0033 0.0034

1/T

Figure 4- ln(Rate) vs 1/T at C=0.08M

Values of K and n
Log(initial rate)= nlog[A] + log[K]
Y=-13.722 x + 32.897
Log K= 32.897
K=1032.897

K=7.8886 ×10 32
n= -13.722

(C= 0.1M):

Table 9-Log[K] and log[rate] at different temperatures at a constant concentration of 0.1M.

Temperature(¿ 0 C)¿ Temperature 1/T Rate (g/m 2 s ) ln(Rate)

) at 0.1M (K)at 0.1M
30 303 0.0033 0.06240 -2.77419
35 308 0.0032 0.09259 -2.37957
40 313 0.0032 0.01010 -4.59522
45 318 0.0031 0.09188 -2.38727

9
 ln(Rate) vs 1/T at C=0.1M
0.00000
-0.50000
-1.00000
-1.50000
ln(Rate)

-2.00000
-2.50000
-3.00000
f(x) = 2142.97278909097 x − 9.93798594606297
-3.50000 R² = 0.0184509002698488
-4.00000
-4.50000
-5.00000
0.0031 0.0032 0.0033 0.0034

1/T

Figure 5- ln(Rate) vs 1/T at C=0.1M

Values of K and n
Log(initial rate)= nlog[A] + log[K]
Y=-6.7284 x + 15.45
Log K= 15.45
K=1015.45

K=2.8184 × 1015
n= -6.7284
Ea
Arrhenius equation lnK= +lnA
RT
Ea
slope=
R
Ea(0.02)= 15.584× 8.314

=129.57J/mol.K

Ea(0.05)= -3.7625× 8.314

=-31.28J/mol.K

Ea(0.08)= -13.722× 8.314

=-114.08J/mol.K

Ea(0.08)= -6.7284× 8.314

=-55.94J/mol.K

10
 6. Discussion of results
The experiment showed that temperature and sulfuric acid concentration have a major impact
on zinc oxide leaching rates. Dissolution rates often increased as acid concentration grew,
which was expected given the increased availability of reactants. However, anomalies were
noted at 0.08M and 0.1M (35°C), where rates suddenly decreased, maybe as a result of
uneven stirring or surface passivation. In contrast to theoretical models, kinetic study
indicated a first-order reaction at 35°C (n ≈ 1.23); nevertheless, other concentrations
produced irregular reaction orders (e.g., n = -3.76 at 0.05M). If reactant concentrations
changed much during sampling, this discrepancy can be the result of the constraints of the
initial rate technique.
Calculations of activation energy (Ea) also showed disparities. Negative Ea values at higher
concentrations (-31.28 to -114.08 J/mol·K) are physically improbable and reflect mistakes in
data interpretation or experimental execution, whereas the 0.02M condition produced a
credible Ea of 129.57 J/mol·K (showing chemical reaction control). Miscalculations of rate
constants (K), non-Arrhenius behavior because to diffusion limits, or temperature changes
during trials are some possible explanations. Zinc's stability in acidic conditions was
validated by thermodynamic analysis using Eh-pH diagrams, which was in line.
The study's contradictory findings show how difficult it is to reconcile kinetic models with
actual systems. For example, rate comparisons may be distorted by different zinc piece
surface areas (e.g., 38–174 m² across trials). According to comparisons with previous
research (e.g., Mukherjee et al., 2014), perfect models frequently overlook real-world
complications like agitation or passivation effects. These results highlight the necessity of
strict variable control in kinetic research.
7. Conclusion
Higher acid concentrations and temperatures generally accelerate dissolving rates, according
to this study's investigation of zinc oxide leaching in sulfuric acid. Zinc's solubility in acidic
environments was confirmed by thermodynamic analysis, and at 35°C, kinetic data partially
matched a first-order model. The application of idealized models to dynamic systems is
limited, though, as evidenced by anomalies in reaction orders and negative activation
energies at specific concentrations. Although contradictory results elsewhere reflect
experimental or computational errors, the 0.02M condition's believable Ea (129.57 J/mol·K)
suggested chemical reaction control.
.
The study emphasizes how thermodynamics and kinetics interact in hydrometallurgy and
how optimizing industrial leaching necessitates striking a balance between operational
realities and reagent efficiency. Although Eh-pH diagrams offer trustworthy thermodynamic
predictions, kinetic parameters must be carefully verified to take mixing and surface area into
consideration. In order to improve predictive models for metal recovery procedures, future
research should consider these disparities.

8. Recommendations
 Experimental Refinements: To reduce variability, standardize the surface areas of
zinc samples and make sure that stirring speeds are constant. For accurate
temperature control, use reactors in controlled environments.

11
  Verification of Data: To resolve negative Ea values, recalculate activation energies
using corrected Arrhenius plots (ln(rate) vs. 1/T). For kinetic modeling, check rate
constant (K) derivations and take nonlinear regression into account.
 Complex Methods: Reduce inaccuracies from discrete sampling by using real-time
monitoring (such as in-situ AAS) to continually follow concentration changes.
 Model Exploration: Examine several kinetic models (such as shrinking core) to take
diffusion constraints into consideration, particularly at higher concentrations when
passivation might take place.
 Industrial Relevance: To replicate real-world settings, scale investigations to pilot
trials while incorporating agitation and particle size effects.
 Error Analysis: To increase the dependability of results, do replicate trials to find
outliers and estimate measurement uncertainties.
 Literature Comparison: To contextualize anomalies and validate procedures,
compare results with research that used comparable methodologies (e.g., Mukherjee
et al., 2014).

9. References
Binnemans, K., & Jones, P. T. (2023). Ionic liquids and Deep-Eutectic solvents in
extractive metallurgy: mismatch between academic research and
industrial applicability. Journal of Sustainable Metallurgy, 9(2), 423-438.
Retrieved from https://link.springer.com/article/10.1007/s40831-023-
00681-6

12
El-Azazy, M., Min, M., & Annus, P. (2020). Electrochemistry. In Electrochemical
Impedance Spectroscopy. Retrieved from
https://www.intechopen.com/books/10054
Mukherjee, S., Mukhopadhyay, S., Hashim, M. A., & Gupta, B. S. (2014).
Contemporary environmental Issues of landfill leachate: Assessment and
Remedies. Critical Reviews in Environmental Science and Technology,
45(5), 472-590. Retrieved from
https://www.tandfonline.com/doi/abs/10.1080/10643389.2013.876524
Paiva, A. P. (2023). Recent Advances in Platinum and Palladium Solvent
Extraction from Real Leaching Solutions of Spent Catalysts. CatalystS,
13(7), 1146. Retrieved from https://www.mdpi.com/2073-4344/13/7/1146
Ploetz, E., Engelke, H., Lächelt, U., & Wuttke, S. (2020). The chemistry of reticular
framework nanoparticles: MOF, ZIF, and COF materials. Advanced
Functional Materials, 30(41). Retrieved from
https://advanced.onlinelibrary.wiley.com/doi/10.1002/adfm.201909062

13